Nitrate and perchlorate salts of nitraza diamines



eta fl gfileral Corporation, Az'usa, Califi, a corporation of No Drawing. Filed Oct. 25, 1957, Set. No.62 ,-964' 20 Claims. or. 260-583) This invention relates to new compositions of matter and a method for their preparation. In particular, the invention relates to bis-inorganic acid salts' er nitraza diamines having the general formula T i 1 .HX XH HzN L A N J A N151: wherein X is a nitrate or perchlorate radical, A and A are alkylene radicals, and n is a whole number from 1 to 6, inclusive.

Due to their high oxygen content, the nitro compounds of this invention are useful as high explosives and can be used in any conventional explosive missile, projectile, rocket, or. the like as the main explosive charge. Ail example of such a missile is disclosed in US. Patent No. 2,470,162, issued May 17, 1949. One way of using the high explosives in a device such as that disclosed in U.S Patent No. 2,470,162 is to pack the crystalline explosive in powder form into the warhead of the missile. Alternatively, the crystals can be first pelletized and then packed. A charge thus prepared is sufficiently insensitive to withstand the shock entailed in the ejection ofa "s'h'e'll from a gun barrel or from a rocket launching tube under the pressure developed from ignition of a propellant charge, and can be caused to explode on operatidri ef'an impactor tirnef us e mechanism firing a detonating explosive such as lead azide or mercury fulrninate.

The compounds of this invention are readilyprepard by treating a nitraza diisocyanate with dilute nitric or perchloric acid, in accordance with the general reaction scheme set forth below:

wherein X, A, A, and n are as defined above.

examples are presented. lt is to be understood, however, that these examples are presented merely as 'a means ;of illustration and are not intended to limit the scope of the invention in any way. r

" 1 ear in Preparationof the bis-nitric acid salt of 3n=itraza-1,5-

pentane diamine 'lna'ro'und bottomha'sk fitted with 'arefiiix condenser, 3-nitraza-1,5-pentane diisocyanate was heated'with areafold excess of 35% nitric acid ona steam bath for a period of 3 hours. The solution was evaporated to dryness in vacuo leaving a quantitative yield of the bis-nitrate salt of 3 -nitraza-l,5-pentane diamine- Upon recrystalliz ation'fioi'nethyl acetate'and ether, the product "exhibited aM.'P of 153 155 C. The elemental analysis of the pioduct'is as follows:

I3, s. 1-s; prcent N, 30565;. 'Feimdgpe'rceni c, 17.66 percent H, 5.11; percent N, 30.78

The explosive power of this compound was calculated to be:

Lead block value 112TNT= 100 Ballistic mortar value 126 TNT=100 EXAMPLE 11 Preparation of the bis-nitric acid salt of 3,6-di nitraz aa 1,8-0ctane diamine The bis-nitric acid salt er 3,6-dinitraza-L8-octafie dia' mine was prepared by reacting 3,6-dinitraza-l,8-octane diisocyanatewith 35% nitric acid according to the procedure described in Example I and recrys'tallizing the product from methanol. The product exhibited .a M.P.

of 18519'0 C. The elemental analysis of the product V is as follows:

. reactio'nof the present invention.

Calculated for C H N O percent C, 19.89; percent H, 5.01; percent N, 30.93. Found: percent C, 20.56; percent H, 5.01; percent N, 30.78

The explosive power of this compound (was found to be:

Lead block value 109 TNT 100 Ballistic mortar value 125 TNT=100 As indicated above, a dilute acid is employed for the By dilute acid, as the term is employed herein, is meant an aqueous solution of acid, preferably of from about 30 to about 85% concentration. The reaction of this invention is a vigorous one and I have found that optimum control can be exerci sed when an acid of about concentration is em,-

ployed in excess. The excess acid acts as a diluent or solvent and thereby effects moderation of the reaction.

Reaction temperature is not critical in the practice of this invention, the only effect of temperaturevariation being a correspondingincrease or decrease in reaction rate/ I have found, however, that elevated reaction temperatures such as "those from ambient toabout 100 C. result in particularly favorable reaction rates and that the reaction pro'ceeds niost efiicaciously at steam bath temperature. 7 V, r .Thenitraza diisocy'anates useful as starting materials for this invention, such as ,3-nitraza-l ,5-pentane"diisocyanate, are prepared by reacting the correspohding diacyl halides, such as 4-nitraza-1,7-heptanedioyl chloridefwith an azide of analkali or alkaline earth metal, such as sodium azide, and subsequently heating under anhydrous Calculated for G l-1 N 03: percent C, 17.52; percent conditions to effect rearrangement to the desired diisocyanate, as more fully disclosed in'assignees 'c'opendingUS. patent appIicatiOnSerialNoJ520,914, filed J1ily 8,fl955.

It will be appreciated that a wide variety 'ofbi s in- To more fully illustrate this invention, the following organic acid salts of nitraza diamines can be prepared in saltscan be readily-obtained' by reacting.the appropriate 1 startingmaterials as, taught herein. s.

This 'application'is a continuation-iii enemy 3 ing US. patent application Serial No. 451,709, filed August 23, 1954, now abandoned.

I claim 1. As new compositions of matter, the bis-inorganic acid salts of nitraza diamines having the general formula:

- N02 XEI-HnN --A-I L I.. wherein X is a radical selected from the group consisting of nitrate and perchlorate radicals; A and A are lower alkylene radicals; and n is a whole number from 1 to 6, inclusive.

2. As new compositions of matter, the bis-nitric acid salts of nitraza diamines having the general formula:

NO: OsNH'H2NAl I L .1 wherein A and A are lower alkylene radicals and n is a whole number from 1 to 6, inclusive.

3. An new compositions of matter. the bis-perchloric acid salts of nitraza diamines having the general formula:

6. As a new composition of matter, the bis-perchloric acid salt of 3-nitraza-l,5-pentane diamine.

7. As a new composition of matter, the bis-perchloric acid salt of 2-nitraza-1,4-butane diamine.

8. As a new composition of matter, the bis-perchloric acid salt of 3,10-dinitraza1,l2-dodecane diamine.

9. As a new composition of matter, the bis-nitric acid salt of 3,6,9-trinitraza-1,1l-undecane diamine having the structural formula:

IYTO: IITO: NI'Oz OsNH-HaN-CH: CHz-N-CHaCHz-N-CH:CHn-N-CHzCHzgNHrHNOs 10. As a new composition of matter, the bis-nitric acid salt of 2,4-dinitraza-l,5-pentane diamine having the structural formula:

11. The method of preparing bis-inorganic acid salts of nitraza diamines having the general formula:

L JD

which comprises reacting a nitraza diisocyanate having the general formula:

NO l I l OCN L A N Jr with a dilute inorganic acid having the general formula HX; wherein X is a radical selected from the group consisting of nitrate and perchlorate radicals, -A and A'- are lower alkylene radicals, and n is a whole number from 1 to 6, inclusive.

At-NCO 4 12. The method of preparing bis-nitric acid salts of nitraza diamines having the general formula:

r il OsNH-HzNT-rA-NT which comprises reacting a nitraza diisocyanate having the general formula:

N0 i I "l ooN L A N J with dilute nitric acid; wherein A and A are lower alkylene radicals and n is a whole number from 1 to 6, inclusive. t

13. The method of preparing bis-perchloric acid salts of nitraza diamines having the general formula:

04ClH-H2NA-N which comprises reacting a nitraza diisocyanate having the general formula:

with dilute perchloric acid; wherein A and A are lower alkylene radicals and n is a whole number from 1 to 6, inclusive.

14. The method of preparing the bis-nitric acid salt of 3-nitraza-l,5-pentane diamine which comprises reacting 3- nitraza-1,5pentane diisocyanate with dilute nitric acid.

15. The method of preparing the bis-nitric acid salt of 3,6-dinitraza-1,8octane diamine which comprises reacting 3,6-dinitraza-1,8-octane diisocyanate with dilute nitric acid.

16. The method of preparing the bis-perchloric acid salt of 3-nitraza-1,5-pentane diamine which comprises reacting 3-nitraza-1,5-pentane diisocyanate with dilute perchloric acid.

17. The method of claim 11 in which the dilute inorganic acid has a concentration of from about 30% to about 18. The method of claim 12 in which the dilute nitric acid has a concentration of about 35%.

19. The method of preparing bis-nitric acid salts of nitraza diamines having the general formula:

which comprises reacting a nitraza diisocyanate having the general formula:

A-NH:HNO:

which comprises reacting a nitraza diisocyanate having the general formula:

L Jr:

with 35% nitric acid, in the presence of dilute nitric acid and on a steam bath; wherein A and A are lower alkylene radicals and n is a whole number from 1 to 6, inclusive.

'-NOO No references cited. 

1. AS NEW COMPOSITIONS OF MATTER, THE BIS-INORGANIC ACID SALTS OF NITRAZA DIAMINES HAVING THE GENERAL FORMULA: 